KR100377305B1 - A Fine Pattern Forming Material And a Process for Manufacturing a Semiconductor Device Using the Same - Google Patents

Abstract

In the formation of the resist pattern by exposure, there is a limit of miniaturization by the wavelength and it has been necessary to overcome this.

Therefore, the present invention coats the frame forming material which receives acid and crosslinks the surface of the underlying resist pattern capable of supplying acid. A predetermined amount of weak acid is added to this frame forming material, or a compound which generates an acid by thermal decomposition is added. An acid is moved to a frame forming material from a base resist pattern by heating, and the crosslinking layer which generate | occur | produced in the interface is formed as a coating layer of a base resist pattern, and a resist pattern is thickened. As a result, the hole diameter and separation width of the resist can be reduced.

Description

A fine pattern forming material and a process for manufacturing a semiconductor device using the same}

The present invention provides a fine separation resist pattern material which reduces the size of the pattern separation or the size of the hole opening when forming the resist pattern in the semiconductor process, a method of forming the fine separation resist pattern using the same, and also the fine separation resist pattern. The manufacturing method of the used semiconductor device, and the semiconductor device manufactured by this manufacturing method are related.

Due to the high integration of semiconductor devices, wiring and separation widths required for manufacturing processes have become very fine. Generally, formation of a fine pattern is performed by the method of forming a resist pattern by the photolithographic technique, and etching the various thin films of a base using the formed resist pattern as a mask.

Therefore, photolithography technology becomes very important in the formation of fine patterns. Photolithography technology consists of resist coating, mask fitting, exposure, and development, and the miniaturization caused by the limitation of the exposure wavelength has occurred.

Moreover, in the conventional lithography process, it is difficult to control the etching resistance of a resist, and it was not possible to control the surface shape, such as roughening the pattern sidewall surface after etching by etching resistance control.

As mentioned above, in the conventional photolithography technique by exposure, the fine pattern formation used for a semiconductor has etched the resist pattern produced by resist coating, exposure, and image development as it is. The pattern size produced by this method is mainly determined by the conditions of resist performance, exposure wavelength, and exposure illumination, and there is no method of obtaining a fine pattern by further forming a frame there. Therefore, the limit of preparation of the first resist pattern was also the limit of preparation of the fine pattern obtained on a semiconductor substrate.

MEANS TO SOLVE THE PROBLEM The present inventors developed the technique disclosed by Unexamined-Japanese-Patent No. 10-73927 in the preceding invention in order to solve the above-mentioned conventional subject.

In this technique, a separate adjusted resist is first applied to the first resist pattern produced by a conventional method, and crosslinked to obtain a crosslinked film. Since this crosslinked film adheres to the first resist pattern interface, the pattern separation width and the hole opening diameter are reduced. As a result, fine pattern creation beyond the limit of the first resist pattern creation can be achieved.

However, in the technique disclosed in the preceding invention, it has been confirmed that a pattern defect such as an opening defect may occur when the concentration of an acid component present in the air of a clean room to be processed increases.

The present invention intends to further improve the technique of the prior invention with respect to such a problem, the object of which is to avoid the occurrence of pattern defects such as opening defects without being affected by the acid component present in the air of the clean room to perform the process, It is an object of the present invention to provide a fine pattern forming material and a method in which an abnormality in an opening dimension due to a local increase in the thickness (frame adhesion amount) of a crosslinked film does not occur.

1 is a mask pattern diagram for explaining a resist pattern forming method of Embodiment 1 of the present invention.

Fig. 2 is a process flowchart for explaining the resist pattern forming method of Embodiment 1 of the present invention.

3 shows an example of a water-soluble resin composition used in the resist pattern forming method of Embodiment 1 of the present invention.

4 is a diagram showing an example of a water-soluble crosslinking agent used in the resist pattern forming method of Embodiment 1 of the present invention.

FIG. 5 is a diagram showing an example of an acid generating compound used in the resist pattern forming method of Embodiment 2 of the present invention. FIG.

<Description of the symbols for the main parts of the drawings>

1: first resist

1a: first resist pattern

2: second layer

2a: second resist pattern

3: semiconductor substrate (semiconductor substrate)

4: crosslinking layer

The fine-pattern forming material of claim 1 is composed of one or more mixtures of water-soluble resins, or a copolymer composed of two or more water-soluble resins as a main component, and a predetermined amount of weak acid is added to the solvent. It is dissolved in water or a mixed solvent of water and a water-soluble organic solvent, and is formed on a first resist pattern for supplying an acid, and a crosslinking reaction is performed at a portion in contact with the first resist pattern by an acid from the first resist pattern. By forming a crosslinked film, the non-crosslinked portion is removed by water or a mixed solvent of water and a water-soluble organic solvent as a developing solution.

The first resist pattern is composed of one or two or more water-soluble crosslinking agents as a main component, and is added by adding a predetermined amount of weak acid and dissolved in water or a mixed solvent of water and a water-soluble organic solvent as a solvent and supplying an acid. And a crosslinking reaction at a portion in contact with the first resist pattern by an acid from the first resist pattern to form a crosslinking film, wherein the non-crosslinking portion is used as a developer in water or a mixed solvent of water and a water-soluble organic solvent. It is characterized by being removed by.

Moreover, it is made by adding one or two or more types of water-soluble resins, and one or two or more types of water-soluble crosslinking agents as a main component, adding a predetermined amount of weak acid, and dissolving it in water or a mixed solvent of water and a water-soluble organic solvent as a solvent, It is formed on a first resist pattern for supplying an acid, and a crosslinking reaction is formed at a portion in contact with the first resist pattern by an acid from the first resist pattern, thereby forming a crosslinking film, and the non-crosslinking portion is water or a developer. It is characterized in that it is removed by a mixed solvent of water and a water-soluble organic solvent.

In addition, the weak acid is characterized by using an appropriate amount of a weak acid of pH 3 or more.

Moreover, it is characterized by using the aromatic carboxylic acid type, such as alkylcarboxylic acid type, such as acetic acid, and benzoic acid, as said weak acid.

The fine-pattern forming material of claim 2 is composed of a water-soluble resin or a mixture of two or more kinds, or a copolymer composed of two or more water-soluble resins as a main component, and a compound which generates an acid by thermal decomposition is added. A portion formed of a first resist pattern which is dissolved in water or a mixed solvent of water and a water-soluble organic solvent as a solvent, and supplies an acid, and is in contact with the first resist pattern by an acid from the first resist pattern A crosslinking film is formed by causing a crosslinking reaction at, and the non-crosslinking portion is removed by water or a mixed solvent of water and a water-soluble organic solvent as a developing solution.

It is also made by adding one or two or more kinds of water-soluble crosslinking agents as a main component and adding a compound that generates an acid by thermal decomposition, and dissolving it in water or a mixed solvent of water and a water-soluble organic solvent as a solvent, and supplying an acid. It is formed on the first resist pattern, and a crosslinking reaction is formed in a portion in contact with the first resist pattern by an acid from the first resist pattern to form a crosslinking film, and the non-crosslinking portion is water or water-soluble organic as a developer. Characterized in that the solvent is removed by a mixed solvent.

Moreover, it is made by adding the compound which produces | generates an acid by thermal decomposition as a main component, and mixes 1 type (s) or 2 or more types of water-soluble resin, 1 type (s) or 2 or more types of water-soluble crosslinking agent, and mixes water or water and a water-soluble organic solvent as a solvent It is formed on a first resist pattern which dissolves in a solvent and supplies an acid, and forms a crosslinking film by causing a crosslinking reaction in a part which contacts the first resist pattern by an acid from the first resist pattern, and a non-crosslinking part. The silver developer is characterized by being removed by water or a mixed solvent of water and a water-soluble organic solvent.

In addition, a diazonium salt containing a counter anion that generates an acid is used as a compound that generates an acid by thermal decomposition.

Moreover, it is characterized by using the anion of an alkyl sulfonic acid type and aromatic sulfonic acid type as a counter anion.

The material for forming the fine pattern of claim 3 is composed mainly of two components of a water-soluble polymer having an ethylene structure in the main chain and a crosslinking agent having an alkoxymethyleneamino group which causes a crosslinking reaction under an acid catalyst. And is dissolved in pure water or a mixed solvent of pure water and a water-soluble organic solvent, and forms a crosslinked film when an acid is supplied.

Moreover, it consists of two components of the water-soluble polymer which has an ethylene structure in a principal chain, and the crosslinking agent which has the alkoxy methyleneamino group which produces a crosslinking reaction under an acid catalyst, and is made by adding the compound which produces | generates an acid by thermal decomposition, and is pure water Or dissolved in a mixed solvent of pure water and a water-soluble organic solvent to form a crosslinked film when acid is supplied.

As the water-soluble polymer, polyvinyl acetal, polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide, polyvinylamine, polyacrylic acid and polyacrylamide may be used alone or in combination of two or more thereof.

As the crosslinking agent, one or a crosslinking agent having an alkoxymethyleneamino group having a melamine derivative and a urea derivative as a skeleton is used.

In addition, the method of manufacturing a semiconductor device of the present invention comprises the steps of forming a first resist pattern capable of supplying an acid on a semiconductor substrate by a first resist, and claim 1 to claim 1 on the first resist pattern. A step of forming a second layer with the fine pattern forming material according to any one of claims 3 to a portion in contact with the first resist pattern of the second layer by supply of an acid from the first resist pattern. A process of forming a crosslinked film, a process of removing a non-crosslinked portion of the second layer to form a second resist pattern, and a process of etching the semiconductor substrate using the second resist pattern as a mask. .

<Embodiment of the invention>

Embodiment 1

1 is a view showing an example of a mask pattern for forming a finely separated resist pattern of the present invention, Figure 1 (a) is a mask pattern 100 of a micro hole, Figure 1 (b) is a The mask pattern 200 and FIG. 1C show the pattern 300 remaining isolated. 2 is a process flowchart for explaining a method for forming a fine separation resist pattern according to the first embodiment of the present invention.

First, with reference to FIG. 1 and FIG. 2, the formation method of the fine-separation resist pattern of this embodiment, and the manufacturing method of the semiconductor device using the same are demonstrated.

First, as shown to Fig.2 (a), the 1st resist 1 which can supply an acid to the semiconductor substrate (semiconductor wafer) 3 is apply | coated (for example, about 0.7-1.0 micrometer in thickness). Various things can be used for the material of this 1st resist 1, and the mechanism which supplies the acid. Details will be described later.

This first resist 1 is applied onto the semiconductor substrate 3 by spin coating or the like, followed by prebaking (heat treatment at about 70 to 110 ° C. for about 1 minute) to remove the solvent in the first resist 1. Evaporate.

Subsequently, in order to form a first resist pattern (base resist pattern), a coated first line such as g line, i line or deep-UV (Deep-UV), KrF excimer, ArF excimer, EB (electron beam), X-ray, etc. Projection exposure is performed using the light source corresponding to the sensitivity wavelength of the resist 1 using the mask containing the pattern shown in FIG.

After exposing the first resist 1, PEB (post-exposure heating) is performed as necessary (for example, PEB temperature: 50 to 130 ° C.) to improve the resolution of the resist 1.

It is then developed using about 0.05 to 3.0 wt% of aqueous alkali solution, such as TMAH (tetramethylammonium hydroxide). 2B shows the thus formed first resist pattern 1a (base resist pattern).

After development, baking may be performed after development as needed (for example, baking temperature is about 60 second at 60-120 degreeC). Since this heat treatment affects the next mixing reaction, it is preferable to set the temperature at an appropriate temperature together with the first resist or the second resist material to be used.

The above process is the same as that of formation of the resist pattern by a general resist process except that the 1st resist 1 which can supply an acid is used.

Subsequently, as shown in Fig. 2 (c), the crosslinking material crosslinked by the presence of an acid on the semiconductor substrate 3 is mainly composed of a fine pattern forming material dissolved in a solvent in which the resist 1 is not dissolved. The 2nd layer 2 is apply | coated by this. The material (material of fine pattern formation) of this 2nd layer 2 is demonstrated in detail later.

The coating method of the second layer 2 is not particularly limited as long as it can be uniformly applied on the first resist pattern 1a, and is applied by spraying, rotating coating, or immersing in the material solution of the second layer (dipping). It is also possible to apply | coat by making it apply.

Next, after application | coating of the 2nd layer 2, this is prebaked as needed (for example, about 85 second at 85 degreeC).

Subsequently, as shown in Fig. 2 (d), the first resist pattern 1a formed on the semiconductor substrate 1 and the second layer 2 formed thereon are heat treated (mixed baking, hereinafter abbreviated as MB if necessary). The heating temperature is, for example, 85 ° C. to 150 ° C.), and the diffusion of acid is promoted in the first resist pattern 1a to be supplied to the second layer 2, and the second layer 2 and the first resist pattern are provided. A crosslinking reaction occurs at the interface of (1a). The mixing baking temperature / time in this case is 85 to 150 degreeC / 60 to 120 second, for example, and what is necessary is just to set it to the optimal conditions by the kind of resist material to be used and the thickness of the reaction layer which are needed.

The crosslinking layer 4 which caused the crosslinking reaction by this mixing baking is formed in the 2nd layer 2 so that the 1st resist pattern 1a may be coat | covered.

Next, as shown in Fig. 2E, the second layer 2, which is not crosslinked, is developed and peeled off using a developer of an aqueous alkali solution such as water or TMAH to form a second resist pattern 2a. Through the above processing, it is possible to obtain a resist pattern in which the hole inner diameter of the hole pattern or the separation width of the line pattern is reduced and the area of the remaining pattern is enlarged in isolation.

Next, the material of the 1st resist 1 and the acid supply method are demonstrated.

The first example is a case where a small amount of acid remaining in the process can be used in the first resist, and in particular, a case in which the remaining acid is moved by means of heating or the like without addition of an acid or an acid generating material.

The second example is a case where some acidic substance is contained inside as the material of the first resist. In this case, it is not necessary to generate an acid by exposure or the like, and it is adjusted to include an acid in the resist material itself, and the acid is diffused and crosslinked by heat treatment. As the acid in this case, for example, a carboxylic acid-based low molecular weight or the like is preferable, but it is not particularly limited as long as it can be mixed in the resist solution.

The third example is a case of having a mechanism for generating an acid therein by suitable heat treatment. In this case, a crosslinking reaction can be implemented only by heat processing, without generating an acid by exposure or the like.

The fourth example is a case where acid is generated by exposure instead of heat treatment.

For example, in the chemically amplified resist, a reaction of generating an acid catalyst by light, electron beam, X-ray or the like occurs, and an amplification reaction caused by the generated acid catalyst is used.

In this case, after application | coating of the 2nd resist 2, it can expose and generate an acid in a 1st resist pattern.

In addition, according to the exposure method, by using an appropriate exposure mask, it is possible to selectively expose the first resist pattern, to form an area that does not crosslink with an area for distinguishing and exposing the exposed part and the non-exposed part.

In addition, this selective exposure can also be performed by irradiating an electron beam.

As a 5th example, after forming a 1st resist pattern, the surface may be surface-treated with an acidic liquid or an acidic gas, and an acid may be diffused and bridge | crosslinked by the heat processing in a next process.

In addition, the material of the first resist 1 may be any of a positive type and a negative type resist as long as it can supply an acid.

As a specific example, the positive resist etc. which are comprised from the mixture of a novolak resin and a naphthoquinone diazide type photosensitive agent are mentioned, for example.

It is also possible to apply a chemically amplified resist using a mechanism for generating an acid.

Next, the material (forming material of a fine pattern) used for the 2nd layer 2 is demonstrated.

As the material of the second layer 2, a crosslinkable water-soluble resin alone or a mixture of two or more thereof can be used as the main component. In addition, a water-soluble crosslinking agent alone or a mixture of two or more thereof is used. In addition, a mixture of these water-soluble resins and water-soluble crosslinking agents is used.

In the present invention, an appropriate weak acid is added to the material of these main components. The purpose of adding an appropriate amount of weak acid is that the material of the second layer is adversely affected by the ambient atmosphere, that is, the acid contained in the air of the clean room, and the pattern defects, the frame formation abnormality (the abnormality in the thickness of the crosslinked film) This is to prevent the possibility of such occurrences. That is, to improve environmental tolerance.

The action of the weak acid addition can be considered as follows. In general, membranes with a pH from acidity are difficult to absorb new acids in the air. This is because, since the acid already exists, the side of the membrane is closer to the concentration equilibrium than the floating acid concentration in the air, so that new acid is difficult to dissolve.

The acid added to the material of the second layer 2 may be a weak acid having a pH of 3 or more, and an appropriate amount thereof is used. A weak acid is preferred if possible. It is preferable to make the concentration into the density | concentration which the material itself of the 2nd layer 2 does not crosslink at normal temperature. For example, the concentration is about 500 ppm with respect to the entire material of the second layer 2. Thereby, the storage stability of the material of the 2nd layer 2 can be ensured.

As a specific example of the acid added to the material of the 2nd layer 2, either or both of alkylcarboxylic acid systems, such as acetic acid, and aromatic carboxylic acid systems, such as benzoic acid, are used as a preferable thing.

The material of the above-mentioned second layer 2 (material of fine pattern formation) dissolves water (for example, pure water) or a mixed solvent of water (for example, pure water) and a water-soluble organic solvent as a solvent. Then, a crosslinked film is formed on the first resist pattern which supplies an acid, and a crosslinking reaction occurs at a portion in contact with the first resist pattern by an acid from the first resist pattern. In addition, the non-crosslinked portion is removed by water or a mixed solvent of water and a water-soluble organic solvent as a developing solution.

In addition, when using the above-mentioned mixture as a main component of the material of the 2nd layer 2, the composition of these materials should just be able to set the optimal composition according to the applied 1st resist material, the set reaction conditions, etc., and it is especially limited. It doesn't happen.

Specific examples of the water-soluble resin composition used as the material of the second layer 2 include polyacrylic acid, polyacrylamide, polyvinyl acetal, polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide, Styrene-maleic acid copolymer, polyvinylamine resin, polyallylamine, oxazoline group-containing water-soluble resin, water-soluble melamine resin, water-soluble urea resin, alkyd resin, sulfonamide resin and the like can be effectively applied. It will not specifically limit, if it is a composition which crosslinks reaction in presence or a composition which can mix with a water-soluble crosslinking agent when a crosslinking reaction does not arise. Moreover, these are used alone or as a mixture, or both are effective.

These water-soluble resins may be used as one kind or as a mixture of two or more kinds, and may be appropriately adjusted according to the reaction amount, reaction conditions, and the like with the underlying first resist 1.

Moreover, these water-soluble resins can also be used as salts, such as hydrochloride, in order to improve the solubility to water.

Subsequently, examples of the water-soluble crosslinking agent that can be used for the material of the second layer 2 include urea-based crosslinking agents such as urea, alkoxymethylene urea, N-alkoxymethylene urea, ethylene urea and ethylene urea carboxylic acid, Melamine crosslinking agents, such as melamine and alkoxymethylene melamine, amino crosslinking agents, such as benzoguanamine and glycoluril, etc. can be used. However, it is not specifically limited to an amino crosslinking agent, and if it is a water-soluble crosslinking agent which crosslinks by an acid, it will not specifically limit.

In addition, as a specific water-soluble resist material used as the material of the second layer 2, it is also effective to mix the water-soluble crosslinking agent alone or a mixture as described above in the water-soluble resin alone or a mixture as described above.

For example, specifically, polyvinyl acetal resin is used as a water-soluble resin composition as a material of the 2nd layer 2, A mixture of methoxymethylol melamine, ethylene urea, etc. is used as a water-soluble crosslinking agent, etc. Can be mentioned. In this case, since water solubility is high, the storage stability of the mixed solution is excellent.

The material applied to the second layer 2 is not particularly limited as long as it is a material that is soluble in a water-soluble solvent that does not dissolve the water-soluble or first resist pattern and at the same time causes a crosslinking reaction in the presence of an acid component.

Incidentally, as described above, the crosslinking reaction can be realized only by heat treatment without generating an acid by re-exposure of the first resist pattern 1a, but in this case, the material of the second layer 2 is highly reactive. It is preferable to select a suitable material and to perform a suitable heat treatment (for example, 85 to 150 degreeC).

In this case, for example, specifically, a mixture of polyvinyl acetal resin and ethylene urea, a mixture of polyvinyl alcohol and ethylene urea, or a water-soluble material composition in which these are mixed at an appropriate ratio is used as the material of the second layer (2). Is valid.

In addition, the formation material of the fine pattern mentioned above can be demonstrated as follows from a separate viewpoint.

That is, examples of suitable materials for forming fine patterns include, as a main component, two components of a water-soluble resin having an ethylene structure in the main chain and a crosslinking agent having an alkoxymethyleneamino group which causes a crosslinking reaction under an acid catalyst. It is made by addition and dissolved in pure water or a mixed solvent of pure water and a water-soluble organic solvent, and forms a crosslinked film when an acid is supplied.

Examples of suitable materials for forming fine patterns include, as a main component, two components of a water-soluble polymer having an ethylene structure in its main chain and a crosslinking agent having an alkoxymethyleneamino group which causes a crosslinking reaction under an acid catalyst. It is made by adding the compound to generate | occur | produce, melt | dissolving in pure water or the mixed solvent of pure water and a water-soluble organic solvent, and when an acid is supplied, it forms a crosslinked film.

In this case, polyvinyl acetal, polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide, polyvinylamine, polyacrylic acid, polyacrylamide, or a mixture of two or more kinds thereof is used as the water-soluble polymer. do.

In addition, the crosslinking agent which used alone or mixed the crosslinking agent which has an alkoxy methylene amino group which has a melamine derivative and a urea derivative as frame | skeleton is used.

Moreover, plasticizers, such as ethylene glycol, glycerin, and triethylene glycol, can also be added to the material of the 2nd layer 2 as an additive.

In order to improve film formation, the material of the second layer 2 is a surfactant, for example, a water-soluble surfactant such as Florade manufactured by 3M, Nonipole manufactured by Sanyo Kasei Co., Ltd., and the like. It may also be added as.

Next, the solvent used for the material (forming material of a fine pattern) of the 2nd layer 2 is demonstrated.

The solvent used for the material of the second layer 2 is preferably water (for example, pure water) or a mixed solvent of water (for example, pure water) and a water-soluble organic solvent.

The solvent used for the material of the second layer 2 needs to dissolve the water-soluble material at the same time without dissolving the pattern 1a of the first resist, but the solvent is not particularly limited as long as it satisfies this.

For example, as a solvent of the material of the second layer 2, water (preferably pure water), a mixed solution of water and an alcohol solvent such as IPA, or a water-soluble organic such as water and N-methylpyrrolidone Mixed solutions of solvents can be used.

It will not specifically limit, if it is water-soluble as a solvent mixed with water, For example, alcohol, such as ethanol, methanol, isopropyl alcohol, (gamma) -butyrolactone, acetone, etc. can be used, It is used for the 2nd layer (2). According to the solubility of a material, it can mix in the range which does not melt the 1st resist pattern 1a.

Next, the specific example in Embodiment 1 is demonstrated.

<Example 1>

200 ppm of acetic acid was added to the material of the second layer 2 (material of fine pattern formation) as described above.

When the sulfuric acid concentration in air of the clean room was 50 ppb using this acid addition material, the above-mentioned crosslinked film formation process was performed.

In the case of using the acid-free material so far, 2000 opening defects occurred, but in the case of using the acid addition material, no opening defects occurred at all.

In this way, a strong fine pattern forming material was obtained with respect to the acid concentration in the air. That is, acid adhesion to the material itself of the second layer 2 was suppressed, and pattern defects and opening dimension abnormalities could be suppressed.

<Example 2>

The material A which added 200 ppm of acetic acid to the material of the 2nd layer 2 was prepared.

For this comparison, material B in which 1000 ppm sulfuric acid was added to the material of the second layer 2 was prepared.

The material A was able to maintain its performance even after 90 days had elapsed, but the material B had a turbidity and the abnormality occurred as the crosslinking of the resin proceeded, thus making the material impossible to use in practice.

In this way, a strong fine pattern formation material was obtained with respect to the acid concentration in the air. In addition, by adding an appropriate amount of weak acid, a stable resist material can be obtained.

That is, acid adhesion to the material itself of the second layer 2 was suppressed, and pattern defects and opening dimension abnormalities could be suppressed. In addition, by using a weak acid having a pH of 3 or more, it was possible to avoid impairing the material stability even if the acid was added to the resist material.

Embodiment 2

EMBODIMENT OF THE INVENTION Below, Embodiment 2 of this invention is described. This Embodiment 2 relates to the material for forming the second resist, and the flow of the crosslinked film formation is the same as that described in Embodiment 1.

In this Embodiment 2, the main component of the material (fine pattern formation material) used for the 2nd layer 2 is the same as that of what was demonstrated in Embodiment 1. And the compound which generate | occur | produces an acid by thermal decomposition is added to the material as a main component. That is, an acid was generated by thermal decomposition of the compound added to the material of the second layer 2 to secure storage stability at room temperature.

The purpose of adding an appropriate amount of such a compound is that the material of the second layer 2 is adversely affected by the acid contained in the ambient atmosphere, i.e., the air of the clean room, during the process, and thus the pattern defect, frame formation abnormality (formation film thickness of crosslinked film) This is to prevent the occurrence of abnormality). That is, to improve environmental tolerance.

Thus, as a compound which generate | occur | produces an acid by heat, the diazonium salt containing the counter anion which produces an acid is used as a preferable example. 5 shows an example of a diazonium salt.

Moreover, as a counter anion of the compound which generates an acid by heat in this way, the thing containing any or both of an anion of an alkyl sulfonic acid type | system | group, an anion of an aromatic sulfonic acid type, or both is used as a preferable example.

When such a compound is added, acid adhesion to the material itself of the second layer 2 can be suppressed, so that pattern defects and opening dimension abnormalities can be suppressed.

In addition, the addition of an acid can be avoided to impair the material stability.

In addition, in the process flow of crosslinked film formation, since no acid is generated until heating, the selection range for the type and concentration of acid to be added is increased without worrying about the adverse effect at the time of normal temperature storage.

Next, the specific example in Embodiment 2 is demonstrated.

<Example 1>

As a material (a fine pattern forming material) of the second layer 2 described in the first embodiment, a material A to which a compound which generates an acid by heat according to the present embodiment is added.

The material B which added the acid itself to the material of the 2nd layer 2 is prepared for this comparison object.

The material A was able to maintain its performance even after 90 days had elapsed, but the material B had a turbidity and the abnormality occurred as the crosslinking of the resin proceeded, thus making the material impossible to use in practice.

In this way, the material strong against the acid concentration in air as a material of the second layer 2 can be obtained. Moreover, even if the compound which generate | occur | produces an acid by heating was added, the stable material was obtained.

As mentioned above, although the formation method which forms a fine isolation resist pattern on the semiconductor substrate 3 was demonstrated in detail, the fine isolation resist pattern of this invention is not limited to the semiconductor substrate 3, According to the manufacturing process of a semiconductor device, It may be formed on insulating layers, such as an oxide film, and may be formed on conductive layers, such as a polysilicon film.

As described above, the formation of the fine-separated resist pattern of the present invention is not limited to the base film, and may be applied in any case as long as it is on a substrate on which the resist pattern can be formed. These are collectively called a semiconductor substrate.

In the present invention, a semiconductor device, such as a semiconductor substrate or various thin films, is etched using the finely divided resist pattern formed as described above as a mask to form a fine space or a minute hole in the semiconductor substrate to form a semiconductor device. To manufacture.

In addition, the present invention includes the following inventions in addition to the inventions described in the claims.

As the water-soluble resin according to claim 1 or 2, polyacrylic acid, polyvinyl acetal, polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide, styrene-maleic anhydride copolymer, poly Formation of a fine pattern mainly composed of vinylamine, polyallylamine, oxazoline group-containing water-soluble resin, water-soluble melamine resin, water-soluble urea resin, alkyd resin, sulfonamide, or a mixture of two or more thereof, or salts thereof material.

The water-soluble crosslinking agent according to claim 1 or 2, wherein the fine pattern comprises a melamine derivative, urea derivative, benzoguanamine, glycoluril, or a mixture of two or more thereof. Forming material.

Further, as the melamine derivative, a fine pattern forming material mainly containing one of melamine and alkoxymethylene melamine or a mixture thereof.

Further, as the urea derivative, a fine-pattern forming material mainly comprising one of urea, alkoxymethylene urea, N-alkoxymethylene urea, ethylene urea carboxylic acid or a mixture of two or more thereof.

As the water-soluble resin according to claim 1 or 2, any one of polyvinyl acetal, polyvinyl alcohol, or a mixture of polyvinyl alcohol and polyvinyl acetal is used, and a melamine derivative and a urea derivative as a water-soluble crosslinking agent. , Or a fine pattern forming material using any one of a melamine derivative and a urea derivative mixture.

The semiconductor device manufactured by invention of the manufacturing method of Claim, or invention of the manufacturing method of each said term | claim.

As described above, according to the present invention, it is possible to obtain a material for forming a fine-separated resist pattern and a method for forming a fine pattern using the same, which enables the formation of a pattern exceeding a wavelength limit in miniaturization of a resist separation pattern and a hole pattern. . In addition, a material for forming a fine separation resist pattern that is stable in the step of forming a crosslinked film can be obtained. Moreover, the material for fine-separation resist pattern formation which has the stability at the time of storage can be obtained.

As a result, the hole diameter of the hole resist pattern can be made smaller than before, and the separation width of the space resist pattern can be made smaller than before.

In addition, the finely divided resist pattern thus formed can be used as a mask to form finely separated spaces or holes on the semiconductor substrate.

In addition, a semiconductor device having spaces or holes finely separated by such a manufacturing method can be obtained.

Claims (3)

(a) 1 type or a mixture of 2 or more types of water-soluble resins, or the copolymer which consists of 2 or more types of said water-soluble resins as a main component, (b) one or more water-soluble crosslinking agents as a main component, or (c) one or two or more water-soluble resins and one or two or more water-soluble crosslinking agents as main components, Made by adding a predetermined amount of weak acid, Crosslinking reaction in a portion which is dissolved in water or a mixed solvent of water and a water-soluble organic solvent as a solvent, is formed on a first resist pattern for supplying an acid, and in contact with the first resist pattern by an acid from the first resist pattern. Forming a crosslinked film, wherein the non-crosslinked portion is removed by water or a mixed solvent of water and a water-soluble organic solvent as a developing solution. Claim 2 was abandoned upon payment of a set-up registration fee. (a) 1 type or a mixture of 2 or more types of water-soluble resins, or the copolymer which consists of 2 or more types of said water-soluble resins as a main component, (b) one or more water-soluble crosslinking agents as a main component, or (c) one or two or more water-soluble resins and one or two or more water-soluble crosslinking agents as main components, By the addition of compounds that generate acids by thermal decomposition, Crosslinking reaction in a portion which is dissolved in water or a mixed solvent of water and a water-soluble organic solvent as a solvent, is formed on a first resist pattern for supplying an acid, and in contact with the first resist pattern by an acid from the first resist pattern. Forming a crosslinked film, wherein the non-crosslinked portion is removed by water or a mixed solvent of water and a water-soluble organic solvent as a developing solution. It is composed mainly of two components of a water-soluble polymer having an ethylene structure in the main chain and a crosslinking agent having an alkoxymethyleneamino group which causes a crosslinking reaction under an acid catalyst, and generates an acid by (a) a predetermined amount of weak acid or (b) thermal decomposition. It is made by adding a compound to dissolve, is dissolved in pure water or a mixed solvent of pure water and a water-soluble organic solvent, is formed on the first resist pattern for supplying an acid, when the acid is supplied to form a crosslinked film Forming material of the pattern.